CN103618100B - Instant hydrogen manufacturing electricity generation system and method - Google Patents
Instant hydrogen manufacturing electricity generation system and method Download PDFInfo
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- CN103618100B CN103618100B CN201310578035.9A CN201310578035A CN103618100B CN 103618100 B CN103618100 B CN 103618100B CN 201310578035 A CN201310578035 A CN 201310578035A CN 103618100 B CN103618100 B CN 103618100B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
- H01M8/0606—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants
- H01M8/0612—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants from carbon-containing material
- H01M8/0618—Reforming processes, e.g. autothermal, partial oxidation or steam reforming
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
- H01M8/04082—Arrangements for control of reactant parameters, e.g. pressure or concentration
- H01M8/04089—Arrangements for control of reactant parameters, e.g. pressure or concentration of gaseous reactants
- H01M8/04104—Regulation of differential pressures
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
- H01M8/04082—Arrangements for control of reactant parameters, e.g. pressure or concentration
- H01M8/04201—Reactant storage and supply, e.g. means for feeding, pipes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/22—Fuel cells in which the fuel is based on materials comprising carbon or oxygen or hydrogen and other elements; Fuel cells in which the fuel is based on materials comprising only elements other than carbon, oxygen or hydrogen
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
Present invention is disclosed a kind of instant hydrogen manufacturing electricity generation system and method, described system comprises hydrogen manufacturing subsystem, power generation sub-system, Collection utilization subsystem, and hydrogen manufacturing subsystem, power generation sub-system, Collection utilization subsystem connect successively; Hydrogen manufacturing subsystem utilizes methanol-water to prepare hydrogen, and obtained hydrogen is used for generating by transfer conduit real-time Transmission to power generation sub-system; Collection utilization subsystem connects the Vent passageway of power generation sub-system, from the gas of discharging, collect water, the raw material of water hydrogen manufacturing subsystem maybe will collected.The present invention can collect the residual air that power generation sub-system is discharged, and therefrom extracts hydrogen, oxygen, water, and hydrogen, oxygen can combustion heat release, and for power generation sub-system provides heat energy, water can transfer to hydrogen manufacturing subsystem and recycle, and system does not need extra water source.The present invention can improve the efficiency of systems generate electricity, saves the energy.
Description
Technical field
The invention belongs to hydrogen preparations and applicatio technical field, relate to a kind of hydrogen gas generating system, particularly relate to a kind of instant hydrogen manufacturing electricity generation system; Meanwhile, the present invention also discloses a kind of instant hydrogen manufacturing electricity-generating method.
Background technology
In numerous new forms of energy, Hydrogen Energy will become the 21 century optimal energy.This is because when burning the coal of identical weight, gasoline and hydrogen, the energy that hydrogen produces is maximum, and the product of its burning is water, does not have lime-ash and waste gas, does not pollute the environment; And coal and oil combustion generate is carbon dioxide and sulfur dioxide, greenhouse effect and acid rain can be produced respectively.Coal and reserves are limited, and hydrogen is mainly stored in water, and after burning, unique product is also water, can produce hydrogen continuously, be finished never.
Hydrogen is a kind of colourless gas.One gram of Hydrogen Energy of burning discharges your heat of 142 kilojoules, is 3 times of gasoline caloric value.The weight of hydrogen is light especially, and it is all lighter than gasoline, natural gas, kerosene many, and thus carrying, transport conveniently, is the most suitable fuel of the high-speed flight such as space flight, the aviation vehicles.Hydrogen can burn in oxygen, and the temperature of hydrogen flame can up to 2500 DEG C, and thus people commonly use hydrogen cutting or weldable steel iron material.
In the Nature, the distribution of hydrogen is very extensive.Water is exactly large " warehouse " of hydrogen, wherein contains the hydrogen of 11%.There is the hydrogen of 1.5% earth Rio; All contain hydrogen in oil, coal, natural gas, animal and plant body etc.The main body of hydrogen exists with the form of compound water, and earth surface about 70% is covered for water, and very greatly, therefore can say, hydrogen is the energy of " inexhaustible, nexhaustible " to moisture storage capacity.If can with suitable method preparing hydrogen from water, so hydrogen also will be the energy that a kind of price is quite cheap.
Having many uses of hydrogen, applicability is strong.It can not only be used as fuel, and metal hydride has the function that chemical energy, heat energy and mechanical energy changes mutually.Such as, hydrogen storage metal has to inhale hydrogen heat release and absorb heat puts the ability of hydrogen, heat storage can be got up, use as heating in room and air-conditioning.
Hydrogen, as gaseous fuel, is first used on automobile.In May, 1976, the U.S. develops a kind of automobile making fuel with hydrogen; Afterwards, Japan also succeeded in developing a kind of take liquified hydrogen as the automobile of fuel; In the latter stage seventies, the Mercedes of front Germany tests hydrogen, and they have only used five kg of hydrogen, just makes running car 110 kilometers.
With hydrogen as motor vehicle fuel, not only totally, easily start at low temperatures, and little to the corrosiveness of engine, the useful life of engine can be extended.Because hydrogen and air can Homogeneous phase mixing, vaporizer used on general automobile can be saved completely, thus the structure of existing automobile can be simplified.More interestingly, if add in the oil 4% hydrogen.Use it as automobile engine fuel, just can fuel-economizing 40%, and without the need to doing great improvement to petrol engine.
Hydrogen is easy to become liquid under certain pressure and temperature, thus that it is all very convenient by iron flask car, on-highway tractor or ship transportation.Liquid hydrogen both can be used as the fuel of automobile, aircraft, also can be used as the fuel of rocket, guided missile.The U.S. is flown to the Apollo Personnel investigation Program of the moon " Long March carrier rocket that number spaceship and China launch a man-made satellite., all make fuel with liquified hydrogen.
In addition, use hydrogen-hydrogen fuel cell Hydrogen Energy directly can also be changed into electric energy, make utilizing of Hydrogen Energy more convenient.At present, this fuel cell is used on spaceship and submarine, and effect is pretty good.Certainly, because cost is higher, be also difficult to generally use for the moment.
The annual production of hydrogen is about 3,600 ten thousand tons in the world now, and wherein the overwhelming majority is produced from oil, coal and natural gas, and this must consume fossil fuel natively very in short supply; Separately have the hydrogen of 4% to be produce by the method for brine electrolysis, but the electric energy consumed is too many, does not calculate very much, therefore, people are trying to explore research hydrogen manufacturing new method.And the energy consumption in Chemical Manufacture can be reduced with methyl alcohol, water reformation hydrogen production and reduce costs, be expected to substitute and be called as the technique of " water electrolysis hydrogen production " of electricity-eating tiger, utilize advanced methanol vapor to reform--pressure swing adsorption making pure hydrogen and be rich in CO
2mist, through further reprocessing, hydrogen and carbon dioxide gas can be obtained simultaneously.
Methyl alcohol and steam pass through catalyst under certain temperature, pressure condition, under the effect of catalyst, the transformationreation of methanol decomposition reaction and carbon monoxide occurs, generates hydrogen and carbon dioxide, this is the gas solid catalytic reaction system of component more than, many reactions.Reactional equation is as follows:
CH
3OH→CO+2H
2(1)
H
2O+CO→CO
2+H
2(2)
CH
3OH+H
2O→CO
2+3H
2(3)
The H that reforming reaction generates
2and CO
2, then through palladium UF membrane by H
2and CO
2be separated, obtain high-purity hydrogen.The power consumption of pressure swing adsorption method is high, equipment large, and is not suitable for the preparation of small-scale hydrogen.
Prepared by existing hydrogen and in electricity generation system, hydrogen gas generation chance discharges some residual air, mainly comprises the hydrogen, oxygen, steam etc. of not yet fully reaction, be nowadays discharged by these gases, and hydrogen is wherein hazardous gas, there is certain potential safety hazard.Meanwhile, these gases have certain value.
In addition, existing hydrogen gas generating system, normally utilizes the hydrogen gas generation prepared, and namely prepares hydrogen and is separated with hydrogen gas generation.First utilize hydrogen producer to prepare hydrogen, hydrogen is positioned in hydrogen gas buffer, then by the hydrogen gas generation in hydrogen gas buffer.The volume of hydrogen gas buffer is comparatively huge, not Portable belt, and mobility is poor, thus constrains the portability of hydrogen preparation and generating equipment.
In view of this, nowadays in the urgent need to designing a kind of new hydrogen gas generating system, to overcome the above-mentioned defect of existing hydrogen gas generating system.
Summary of the invention
Technical problem to be solved by this invention is: provide a kind of instant hydrogen manufacturing electricity generation system, effectively can utilize the residual air after power generation sub-system, improve the efficiency of system.
In addition, the present invention also provides a kind of instant hydrogen manufacturing electricity-generating method, effectively can utilize the residual air after power generation sub-system, improve the efficiency of system.
For solving the problems of the technologies described above, the present invention adopts following technical scheme:
A kind of instant hydrogen manufacturing electricity generation system, described system comprises: hydrogen manufacturing subsystem, air pressure adjustment subsystem, power generation sub-system, Collection utilization subsystem, and hydrogen manufacturing subsystem, air pressure adjustment subsystem, power generation sub-system, Collection utilization subsystem connect successively;
Described hydrogen manufacturing subsystem utilizes methanol-water to prepare hydrogen, and described hydrogen manufacturing subsystem comprises solid hydrogen reservoir vessel, liquid container, raw material conveying device, hydrogen producer, membrane separation device;
Described hydrogen producer comprises heat exchanger, vaporizer, reformer chamber; Membrane separation device is arranged in separation chamber, and separation chamber is arranged at the inside of reformer chamber;
Described solid hydrogen reservoir vessel, liquid container are connected with hydrogen producer respectively; Liquid first alcohol and water is stored in liquid container;
Store solid hydrogen in described solid hydrogen reservoir vessel, when hydrogen generating system starts, by gasification module, solid hydrogen is converted to gaseous hydrogen, gaseous hydrogen passes through combustion heat release, for hydrogen producer provides startup heat energy, as the startup energy of hydrogen producer;
First alcohol and water in described liquid container is delivered to heat exchanger heat exchange by raw material conveying device, enters vaporizer gasification after heat exchange;
Methanol vapor after gasification and steam enter reformer chamber, and reformer chamber is provided with catalyst, and reformer chamber bottom and middle portion temperature are 300 DEG C ~ 420 DEG C;
The temperature on described reformer chamber top is 400 DEG C ~ 570 DEG C; Reformer chamber is connected by connecting line with separation chamber, all or part of top being arranged at reformer chamber of connecting line, and the high temperature by reformer chamber top continues the gas that heating exports from reformer chamber; Described connecting line, as the buffering between reformer chamber and separation chamber, makes the temperature of the gas exported from reformer chamber identical with the temperature of separation chamber or close;
Temperature in described separation chamber is set as 350 DEG C ~ 570 DEG C; Be provided with membrane separator in separation chamber, obtain hydrogen from the aerogenesis end of membrane separator;
Described raw material conveying device provides power, by the feedstock transportation in liquid container to hydrogen producer; Described raw material conveying device provides the pressure of 0.15 ~ 5MPa to raw material, and the hydrogen that hydrogen producer is obtained has enough pressure;
After described hydrogen producer starts hydrogen manufacturing, the hydrogen partial that hydrogen producer is obtained is or/and residual air is run by burning maintenance hydrogen producer;
The hydrogen that described hydrogen producer obtains is delivered to membrane separation device and is separated, and is more than or equal to 0.7MPa for separating of the difference of pressure inside and outside the membrane separation device of hydrogen;
Described membrane separation device is the membrane separation device at porous ceramic surface Vacuum Deposition palladium-silver, and film plating layer is palladium-silver, and the mass percent palladium of palladium-silver accounts for 75% ~ 78%, and silver accounts for 22% ~ 25%;
Obtained hydrogen is passed through transfer conduit real-time Transmission to power generation sub-system by described hydrogen manufacturing subsystem; Described transfer conduit is provided with air pressure adjustment subsystem, for adjusting the air pressure in transfer conduit; The hydrogen gas generation that described power generation sub-system utilizes hydrogen manufacturing subsystem obtained;
Described air pressure adjustment subsystem comprises microprocessor, gas pressure sensor, valve positioner, air outlet valve, outlet pipe; Described gas pressure sensor is arranged in transfer conduit, in order to respond to the barometric information in transfer conduit, and the barometric information of induction is sent to microprocessor; This barometric information received from gas pressure sensor and setting threshold interval are compared by described microprocessor; When the pressure data received is higher than the maximum in setting threshold interval, Microprocessor S3C44B0X valve positioner opens air outlet valve setting-up time, air pressure in transfer conduit is made to be in setting range, one end of outlet pipe connects air outlet valve simultaneously, the other end connects described hydrogen manufacturing subsystem, and the firing equipment that needs being hydrogen manufacturing subsystem by burning heats; When the pressure data received is lower than the minimum value in setting threshold interval, hydrogen manufacturing subsystem described in Microprocessor S3C44B0X accelerates the transporting velocity of raw material;
Described Collection utilization subsystem connects the Vent passageway of power generation sub-system, from the gas of discharging, collect water, utilizes the water collected as the raw material of hydrogen manufacturing subsystem, thus recycles;
Described Collection utilization subsystem comprises hydrogen separator, hydrogen check-valves, oxygen separator, oxygen check valve, is separated by hydrogen, oxygen is separated with water with water.
A kind of instant hydrogen manufacturing electricity generation system, described system comprises: hydrogen manufacturing subsystem, power generation sub-system, Collection utilization subsystem, and hydrogen manufacturing subsystem, power generation sub-system, Collection utilization subsystem connect successively;
Described hydrogen manufacturing subsystem utilizes methanol-water to prepare hydrogen, and obtained hydrogen is used for generating by transfer conduit real-time Transmission to power generation sub-system;
Described Collection utilization subsystem connects the Vent passageway of power generation sub-system, from the gas of discharging, collect water, the raw material of water hydrogen manufacturing subsystem maybe will collected.
As a preferred embodiment of the present invention, described Collection utilization subsystem comprises air-water separator, the water collected is delivered to hydrogen manufacturing subsystem, thus recycles.
As a preferred embodiment of the present invention, described Collection utilization subsystem comprises hydrogen separator, hydrogen check-valves, and the Vent passageway of power generation sub-system connects the entrance of hydrogen separator, is provided with hydrogen check-valves in the pipeline that hydrogen separator exit connects; Described hydrogen separator is for separating of hydrogen and water.
As a preferred embodiment of the present invention, described Collection utilization subsystem also comprises hydrogen/oxygen separator, for separating of hydrogen and oxygen; Hydrogen/oxygen separator is arranged between described power generation sub-system Vent passageway and hydrogen separator.
As a preferred embodiment of the present invention, described Collection utilization subsystem also comprises oxygen separator, oxygen check valve, for collecting oxygen;
The hydrogen that described Collection utilization subsystem is collected and oxygen for hydrogen manufacturing subsystem or/and power generation sub-system.
A preparing hydrogen, generating power method for said system, described preparing hydrogen, generating power method comprises the steps:
Described hydrogen manufacturing subsystem utilizes methanol-water to prepare hydrogen, obtained hydrogen is passed through transfer conduit real-time Transmission to power generation sub-system;
The hydrogen gas generation that described power generation sub-system utilizes hydrogen manufacturing subsystem obtained;
Described Collection utilization subsystem connects the Vent passageway of power generation sub-system, from the gas of discharging, collect water, the raw material of water hydrogen manufacturing subsystem maybe will collected.
As a preferred embodiment of the present invention, described method also comprises: oxygen Collection utilization step, collects oxygen by Collection utilization subsystem; By the hydrogen collected and oxygen for hydrogen manufacturing subsystem or/and power generation sub-system.
As a preferred embodiment of the present invention, described method also comprises: described method also comprises: Hydrogen collection utilizes step, collects hydrogen by Collection utilization subsystem; By the hydrogen collected and oxygen for hydrogen manufacturing subsystem or/and power generation sub-system.
Beneficial effect of the present invention is: the instant hydrogen manufacturing electricity generation system that the present invention proposes and method, the residual air that power generation sub-system is discharged can be collected, and therefrom extract hydrogen, oxygen, water, hydrogen, oxygen can combustion heat release, for power generation sub-system provides heat energy, water can transfer to hydrogen manufacturing subsystem and recycle, and system does not need extra water source.The present invention can improve the efficiency of systems generate electricity, saves the energy.
In addition, the hydrogen gas generation that the present invention can also utilize immediate system standby, without the need to hydrogen gas buffer, by the hydrogen gas pressure in air pressure adjustment subsystem adjustment transfer conduit; Because the volume of air pressure adjustment subsystem is very little, portability, the mobility of preparing hydrogen, generating power system thus can be improved further.
Accompanying drawing explanation
Fig. 1 is the composition schematic diagram of the instant hydrogen manufacturing electricity generation system of the present invention in embodiment one.
Fig. 2 is the operating diagram of Collection utilization subsystem in embodiment one.
Fig. 3 is the composition schematic diagram of the instant hydrogen manufacturing electricity generation system of the present invention in embodiment two.
Fig. 4 is the composition schematic diagram of hydrogen manufacturing subsystem in embodiment three.
Fig. 5 is the composition schematic diagram of hydrogen manufacturing subsystem in embodiment four.
Fig. 6 is the structural representation of the first starting drive in embodiment four.
Embodiment
The preferred embodiments of the present invention are described in detail below in conjunction with accompanying drawing.
Embodiment one
Refer to Fig. 1, present invention is disclosed a kind of instant hydrogen manufacturing electricity generation system, described system comprises: hydrogen manufacturing subsystem 100, power generation sub-system 300, Collection utilization subsystem 400, and hydrogen manufacturing subsystem 100, power generation sub-system 200, Collection utilization subsystem 400 connect successively;
Described hydrogen manufacturing subsystem 100 utilizes methanol-water to prepare hydrogen, and obtained hydrogen is used for generating by transfer conduit real-time Transmission to power generation sub-system 300;
Described Collection utilization subsystem 400 connects the Vent passageway of power generation sub-system 300, from the gas of discharging, collect hydrogen, or utilizes the hydrogen collected for hydrogen manufacturing subsystem 100 or/and power generation sub-system 300.
As shown in Figure 2, described Collection utilization subsystem 400 comprises hydrogen separator 401, hydrogen check-valves 402, the Vent passageway of power generation sub-system 300 connects the entrance of hydrogen separator 401, is provided with hydrogen check-valves 402, prevents hydrogen from pouring in down a chimney in the pipeline that hydrogen separator 401 exit connects; Described hydrogen separator 401 is for separating of hydrogen and water.In addition, described Collection utilization subsystem also comprises hydrogen/oxygen separator, for separating of hydrogen and oxygen; Hydrogen/oxygen separator is arranged between described power generation sub-system Vent passageway and hydrogen separator.
In the present embodiment, described Collection utilization subsystem 400 also comprises oxygen separator 411, oxygen check valve 412, for collecting oxygen.The hydrogen that described Collection utilization subsystem 400 is collected and oxygen, for hydrogen manufacturing subsystem 100, also can be used for power generation sub-system 300 to use.In addition, the oxygen collected can be deposited in setting container, for people's oxygen uptake; The water collected can be used for people to drink.
Because described Collection utilization subsystem comprises air-water separator (as above-mentioned hydrogen separator, oxygen separator), therefore water can be collected (than the also many several times of the moisture in raw material, because also containing hydrogen atom in methyl alcohol, water is obtained with oxygen reaction) after obtained hydrogen, water is delivered to hydrogen manufacturing subsystem 100, raw water can recycle, without the need to other interpolation.
Therefore, present system can collect the utilities such as hydrogen, oxygen, water from the residual air of power generation sub-system, can improve the generating efficiency of system, simultaneously conservation (water).
Embodiment two
The difference of the present embodiment and embodiment one is, in the present embodiment, refer to Fig. 3, the instant hydrogen manufacturing electricity generation system of the present invention comprises hydrogen manufacturing subsystem 100, air pressure adjustment subsystem 200, power generation sub-system 300, and hydrogen manufacturing subsystem 100, air pressure adjustment subsystem 200, power generation sub-system 300 connect successively.Described hydrogen manufacturing subsystem 100 utilizes methanol-water to prepare hydrogen, obtained hydrogen is passed through transfer conduit real-time Transmission to power generation sub-system 300; Described transfer conduit is provided with air pressure adjustment subsystem 200, for adjusting the air pressure in transfer conduit; The hydrogen gas generation that described power generation sub-system 300 utilizes hydrogen manufacturing subsystem obtained.
Described hydrogen manufacturing subsystem utilizes methanol-water to prepare hydrogen, and described hydrogen manufacturing subsystem comprises solid hydrogen reservoir vessel, liquid container, raw material conveying device, hydrogen producer, membrane separation device.
As shown in Figure 3, described air pressure adjustment subsystem 200 comprises microprocessor 21, gas pressure sensor 22, valve positioner 23, air outlet valve 24, outlet pipe 25.Described gas pressure sensor 22 is arranged in transfer conduit, in order to respond to the barometric information in transfer conduit, and the barometric information of induction is sent to microprocessor 21; This barometric information received from gas pressure sensor 22 and setting threshold interval are compared by described microprocessor 21, and control the switch of air outlet valve 24 with this.When the pressure data received is higher than the maximum in setting threshold interval, air outlet valve setting-up time opened by microprocessor 21 by-pass valve control controller 23, air pressure in transfer conduit is made to be in setting range. preferably, one end of outlet pipe 25 connects air outlet valve 24, the other end connects described hydrogen manufacturing subsystem 100, and the firing equipment (as reformer chamber) that needs being hydrogen manufacturing subsystem 100 by burning heats; When the pressure data received is lower than the minimum value in setting threshold interval, microprocessor 21 controls the transporting velocity that described hydrogen manufacturing subsystem 100 accelerates raw material, thus improves hydrogen manufacturing speed.
Be described above the instant hydrogen manufacturing electricity generation system of the present invention, the present invention is while the above-mentioned instant hydrogen manufacturing electricity generation system of announcement, and also disclose a kind of electricity-generating method of above-mentioned instant hydrogen manufacturing electricity generation system, described electricity-generating method comprises:
[step S1] described hydrogen manufacturing subsystem utilizes methanol-water to prepare hydrogen, obtained hydrogen is passed through transfer conduit real-time Transmission to power generation sub-system.
The process that described hydrogen manufacturing subsystem prepares hydrogen comprises:
Store solid hydrogen in solid hydrogen reservoir vessel, when hydrogen generating system starts, by gasification module, solid hydrogen is converted to gaseous hydrogen, gaseous hydrogen passes through combustion heat release, for hydrogen producer provides startup heat energy, as the startup energy of hydrogen producer;
Described raw material conveying device provides power, by the feedstock transportation in liquid container to hydrogen producer; Described raw material conveying device provides the pressure of 0.15 ~ 5MPa to raw material, and the hydrogen that hydrogen producer is obtained has enough pressure;
Hydrogen prepared by hydrogen producer;
The hydrogen that described hydrogen producer obtains is delivered to membrane separation device and is separated, and is more than or equal to 0.7MPa(as 1.1MPa for separating of the difference of pressure inside and outside the membrane separation device of hydrogen).
[step S2] described transfer conduit is provided with air pressure adjustment subsystem, the air pressure in adjustment transfer conduit; Described gas pressure sensor is arranged in transfer conduit, the barometric information in induction transfer conduit, and the barometric information of induction is sent to microprocessor; Described microprocessor controls the switch of air outlet valve according to the barometric information that described gas pressure sensor is responded to.
Described air pressure adjustment subsystem specifically comprises when carrying out air pressure adjustment: compare in the barometric information that described gas pressure sensor is responded to by described microprocessor and setting threshold interval; When the pressure data received is higher than the maximum in setting threshold interval, Microprocessor S3C44B0X valve positioner opens air outlet valve setting-up time, makes air pressure in transfer conduit be in setting range; When the pressure data received is lower than the minimum value in setting threshold interval, hydrogen manufacturing subsystem described in Microprocessor S3C44B0X accelerates the transporting velocity of raw material.
The hydrogen gas generation that [step S3] described power generation sub-system utilizes hydrogen manufacturing subsystem obtained.
Embodiment three
The difference of the present embodiment and embodiment one is, in the present embodiment, refer to Fig. 4, described hydrogen manufacturing subsystem utilizes methanol-water to prepare hydrogen, and described hydrogen manufacturing subsystem comprises solid hydrogen reservoir vessel 80, liquid container 10, raw material conveying device 50, hydrogen producer 20, membrane separation device 30.
Described solid hydrogen reservoir vessel 80, liquid container 10 are connected with hydrogen producer 20 respectively; Store liquid first alcohol and water in liquid container 10, in described solid hydrogen reservoir vessel 80, store solid hydrogen.
When hydrogen generating system starts, by gasification module, the solid hydrogen in solid hydrogen reservoir vessel 80 is converted to gaseous hydrogen, gaseous hydrogen passes through combustion heat release, for hydrogen producer 20 provides startup heat energy, as the startup energy of hydrogen producer 20.Certainly, solid hydrogen reservoir vessel 80 is not necessaries of the present invention, can start hydrogen producer 20 by other energy.
Described raw material conveying device 50 provides power, by the feedstock transportation in liquid container 10 to hydrogen producer 20; Described raw material conveying device 50 provides the pressure of 0.15 ~ 5MPa (as providing the pressure of 0.2MPa or 1.1MPa or 1.2MPa or 1.5MPa or 5MPa) to raw material, makes the obtained hydrogen of hydrogen producer 20 have enough pressure.After described hydrogen producer 20 starts hydrogen manufacturing, the hydrogen partial that hydrogen producer 20 is obtained is or/and residual air is run (certainly, the operation of hydrogen producer 20 can also pass through other energy) by burning maintenance hydrogen producer 20.
The hydrogen that described hydrogen producer 20 obtains is delivered to membrane separation device 30 and is separated, and being more than or equal to 0.7MPa(such as pressure inside and outside membrane separation device 30 for separating of the difference of pressure inside and outside the membrane separation device 30 of hydrogen is 0.7MPa or 1.1MPa or 1.2MPa or 1.5MPa or 5MPa).
In the present embodiment, described membrane separation device 30 is the membrane separation device at porous ceramic surface Vacuum Deposition palladium-silver, and film plating layer is palladium-silver, and the mass percent palladium of palladium-silver accounts for 75% ~ 78%, and silver accounts for 22% ~ 25%.The preparation technology of described membrane separation device 30 comprises the steps:
Step 1, porous ceramic is arranged in the vacuum chamber of magnetic control sputtering device;
Step 2, utilize magnetic control sputtering device magnetic field generation mechanisms produce magnetic field, make metallic target produce offset current, metallic target as negative pole, thus makes porous ceramic surface with magnetosphere body; The material of described metallic target is sputtering precious metal, and described precious metal is palladium-silver, and mass percent palladium accounts for 75% ~ 78%, and silver accounts for 22% ~ 25%;
Step 3, produce while offset current at metallic target, heat the vacuum chamber of magnetic control sputtering device, temperature controls at 350 DEG C ~ 800 DEG C;
Step 4, the gas extracted out in vacuum chamber, the vacuum degree when vacuum indoor is less than 10
-2during Pa, in vacuum chamber, be filled with the argon gas of setting concentration;
Step 5, pass into electric current to metallic target, carry out sputter coating; The ion that metallic target produces accelerates to fly in the process of porous ceramic surface to collide with ar atmo under the effect of electric field, and ionize out a large amount of argon ions and electronics, electronics flies to porous ceramic surface; Argon ion accelerates to bombard metallic target under the effect of electric field, sputters a large amount of metallic target target atom or molecule, and the target atom in neutrality or molecule deposition, on porous ceramic surface, form the precious metal film of 1 ~ 15 μm;
Wherein, in the process of sputter coating, argon concentration detecting step is also comprised; Detect the argon concentration in vacuum chamber in real time or with setting-up time interval, when argon concentration opens argon gas charging valve automatically lower than during setting threshold, in vacuum chamber, be filled with argon gas, until the argon concentration in vacuum chamber meets setting threshold scope;
Air pressure detecting step is also comprised in the process of sputter coating; Detect the air pressure in vacuum chamber in real time or with setting-up time interval, when the air pressure of vacuum indoor is not interval at setting threshold, the air pressure in adjustment vacuum chamber is interval to setting threshold;
Step 6, in vacuum chamber, pass into air, take out workpiece.
Preferably, described hydrogen producer comprises heat exchanger, vaporizer, reformer chamber; Membrane separation device is arranged in separation chamber, and separation chamber is arranged at the top of reformer chamber.
First alcohol and water in described liquid container is delivered to heat exchanger heat exchange by raw material conveying device, enters vaporizer gasification after heat exchange; Methanol vapor after gasification and steam enter reformer chamber, and reformer chamber is provided with catalyst, and reformer chamber bottom and middle portion temperature are 350 DEG C ~ 409 DEG C; The temperature on described reformer chamber top is 400 DEG C ~ 570 DEG C; Reformer chamber is connected by connecting line with separation chamber, all or part of top being arranged at reformer chamber of connecting line, and the high temperature by reformer chamber top continues the gas that heating exports from reformer chamber; Described connecting line, as the buffering between reformer chamber and separation chamber, makes the temperature of the gas exported from reformer chamber identical with the temperature of separation chamber or close; Temperature in described separation chamber is set as 400 DEG C ~ 570 DEG C; Be provided with membrane separator in separation chamber, obtain hydrogen from the aerogenesis end of membrane separator.
Be described above the composition of methanol-water hydrogen manufacturing subsystem, the present invention also discloses a kind of hydrogen production process utilizing above-mentioned methanol-water hydrogen manufacturing subsystem, and described hydrogen production process comprises:
Solid hydrogen is stored in [step 0] described solid hydrogen reservoir vessel, when hydrogen generating system starts, by gasification module, solid hydrogen is converted to gaseous hydrogen, gaseous hydrogen passes through combustion heat release, for hydrogen producer provides startup heat energy, as the startup energy of hydrogen producer;
[step 1] described raw material conveying device provides power, by the feedstock transportation in liquid container to hydrogen producer; Described raw material conveying device provides the pressure of 0.15 ~ 5MPa to raw material, and the hydrogen that hydrogen producer is obtained has enough pressure;
Hydrogen prepared by [step 2] hydrogen producer; Specifically comprise:
First alcohol and water in described liquid container is delivered to heat exchanger heat exchange by raw material conveying device, enters vaporizer gasification after heat exchange;
Methanol vapor after gasification and steam enter reformer chamber, and reformer chamber is provided with catalyst, and reformer chamber bottom and middle portion temperature are 300 DEG C ~ 420 DEG C;
The temperature on described reformer chamber top is 400 DEG C ~ 570 DEG C; Reformer chamber is connected by connecting line with separation chamber, all or part of top being arranged at reformer chamber of connecting line, and the high temperature by reformer chamber top continues the gas that heating exports from reformer chamber; Described connecting line, as the buffering between reformer chamber and separation chamber, makes the temperature of the gas exported from reformer chamber identical with the temperature of separation chamber or close;
Temperature in described separation chamber is set as 350 DEG C ~ 570 DEG C; Be provided with membrane separator in separation chamber, obtain hydrogen from the aerogenesis end of membrane separator.
The hydrogen that [step 3] described hydrogen producer obtains is delivered to membrane separation device and is separated, and is more than or equal to 0.7MPa for separating of the difference of pressure inside and outside the membrane separation device of hydrogen;
In the present embodiment, separation chamber is arranged at the top of reformer chamber by hydrogen manufacturing subsystem, the temperature that middle part and bottom are compared in reformer chamber top is higher, reformer chamber and separation chamber is connected by connecting line, the gas that connecting line can utilize the high-temperature heating on reformer chamber top to carry in the process of conveying, play pre-heat effect, mode of heating is very convenient simultaneously.Pipeline between reformer chamber and separation chamber, as preheating temperature control mechanism, can heat the gas exported from reformer chamber, makes the temperature of the gas exported from reformer chamber identical with the temperature of separation chamber or close; Thus the low temperature requirements of reformer chamber catalyst can be ensured respectively, and the high temperature requirement of separation chamber, and then improve hydrogen preparation efficiency.
Embodiment four
The difference of the present embodiment and embodiment three is, in the present embodiment, hydrogen manufacturing subsystem does not arrange solid hydrogen reservoir vessel 80, refers to Fig. 5, and hydrogen manufacturing subsystem comprises: liquid container 10, raw material conveying device 50, device for rapidly starting, hydrogen producer 20, membrane separation device 30.Described device for rapidly starting provides the startup energy for hydrogen producer; Described device for rapidly starting comprises the first starting drive 40, second starting drive 60.
As shown in Figure 6, the internal diameter that described first starting drive 40 comprises housing 41, first heating arrangements 42, first gasification pipe 43, first gasification pipe 43 is 1 ~ 2mm, and the first gasification pipe 43 is closely wound on the first heating arrangements 42; First heating arrangements 42 can be electrically heated rod, utilizes alternating current or storage battery, dry cell.
One end of described first gasification pipe 43 connects liquid container 10, and methyl alcohol is admitted in the first gasification pipe 43; The other end of the first gasification pipe 43 exports vaporized methyl alcohol, then by ignition mechanism ignition; Or the other end of the first gasification pipe 43 exports vaporized methyl alcohol, and the methanol temperature exported reaches self-ignition point, and methyl alcohol exports rear direct spontaneous combustion from the first gasification pipe 43.
Described second starting drive 60 comprises the second gasification pipe, and the main body of the second gasification pipe is arranged at described reformer chamber, and the second gasification pipe is reformer chamber heating (can also be the heating of other unit of hydrogen generating system).First gasification pipe 43 is or/and the methyl alcohol that the second gasification pipe exports is heat the second gasification pipe, by the methanol gasifying in the second gasification pipe while reformer chamber heats.
First, the methyl alcohol needing the first gasification pipe 43 to export heats the second gasification pipe, setting-up time after the methyl alcohol that the second gasification pipe can continue generation gasification, can select closedown first starting drive 40, and the methyl alcohol exported by the second gasification pipe is the second gasification pipe heating; The dependence to extra power can be reduced so further.
Referring to Fig. 6, in order to improve the firing rate of hydrogen producer, being provided with heating pipe line 21 at the reformer chamber inwall of described hydrogen producer 20, in heating pipe line 21, be placed with catalyst (as can by heating and temperature control at 380 DEG C ~ 480 DEG C); Described device for rapidly starting 40 is reformer chamber heating by the described heating pipe line 21 of heating, can improve the efficiency of heating surface.
After described hydrogen generating system starts, hydrogen generating system provides the energy needed for operation by the hydrogen that hydrogen producer obtains; Now, device for rapidly starting can be closed.
Be described above the composition of Methanol water hydrogen production system of the present invention, the present invention is while the above-mentioned hydrogen generating system of announcement, and also disclose a kind of hydrogen production process of above-mentioned Methanol water hydrogen production system, described method comprises the steps:
[step S1] be setting up procedure fast; Described hydrogen generating system utilizes device for rapidly starting to provide the startup energy to start.Specifically comprise:
First heating arrangements energising setting-up time of the first starting drive, reaches after design temperature until the first heating arrangements and passes into methyl alcohol to the first gasification pipe; Because the first gasification pipe is closely wound on the first heating arrangements, methanol temperature progressively raises; First gasification pipe exports vaporized methyl alcohol, then by ignition mechanism ignition; Or the first gasification pipe exports vaporized methyl alcohol, and the methanol temperature exported reaches self-ignition point, directly spontaneous combustion after methyl alcohol exports from the first gasification pipe;
The methyl alcohol of gasification passes through combustion heat release, for hydrogen producer provides the startup energy; Meanwhile, the methyl alcohol burning that the first gasification pipe exports is also the second gasification pipe heating of the second starting drive, by the methanol gasifying in the second gasification pipe;
After exporting the methyl alcohol of gasification in the second gasification pipe, close the first starting drive, the methyl alcohol exported by the second gasification pipe of the second starting drive is that reformer chamber heats, and heats the second gasification pipe, by the methanol gasifying in the second gasification pipe simultaneously; Described reformer chamber inwall is provided with heating pipe line, is placed with catalyst in heating pipe line; Described device for rapidly starting is reformer chamber heating by the described heating pipe line of heating.
After [step S2] system starts, hydrogen generating system provides the energy needed for operation by the hydrogen that hydrogen producer obtains; Treat that hydrogen generating system runs obtained enough hydrogen, close device for rapidly starting; The hydrogen partial obtained by hydrogen producer is or/and residual air maintains hydrogen producer operation by burning.
In sum, the instant hydrogen manufacturing electricity generation system that the present invention proposes and method, the residual air that power generation sub-system is discharged can be collected, and therefrom extract hydrogen, oxygen, water, hydrogen, oxygen can combustion heat release, for power generation sub-system provides heat energy, water can transfer to hydrogen manufacturing subsystem and recycle, and system does not need extra water source.The present invention can improve the efficiency of systems generate electricity, saves the energy.
Here description of the invention and application is illustrative, not wants by scope restriction of the present invention in the above-described embodiments.Distortion and the change of embodiment disclosed are here possible, are known for the replacement of embodiment those those of ordinary skill in the art and the various parts of equivalence.Those skilled in the art are noted that when not departing from spirit of the present invention or substantive characteristics, the present invention can in other forms, structure, layout, ratio, and to realize with other assembly, material and parts.When not departing from the scope of the invention and spirit, can other distortion be carried out here to disclosed embodiment and change.
Claims (3)
1. an instant hydrogen manufacturing electricity generation system, it is characterized in that, described system comprises: hydrogen manufacturing subsystem, air pressure adjustment subsystem, power generation sub-system, Collection utilization subsystem, and hydrogen manufacturing subsystem, air pressure adjustment subsystem, power generation sub-system, Collection utilization subsystem connect successively;
Described hydrogen manufacturing subsystem utilizes methyl alcohol, water prepares hydrogen, and described hydrogen manufacturing subsystem comprises solid hydrogen reservoir vessel, liquid container, raw material conveying device, hydrogen producer, membrane separation device;
Described hydrogen producer comprises heat exchanger, vaporizer, reformer chamber; Membrane separation device is arranged in separation chamber, and separation chamber is arranged at the inside of reformer chamber;
Described solid hydrogen reservoir vessel, liquid container are connected with hydrogen producer respectively; Liquid first alcohol and water is stored in liquid container;
Store solid hydrogen in described solid hydrogen reservoir vessel, when hydrogen generating system starts, by gasification module, solid hydrogen is converted to gaseous hydrogen, gaseous hydrogen passes through combustion heat release, for hydrogen producer provides startup heat energy, as the startup energy of hydrogen producer;
First alcohol and water in described liquid container is delivered to heat exchanger heat exchange by raw material conveying device, enters vaporizer gasification after heat exchange;
Methanol vapor after gasification and steam enter reformer chamber, and reformer chamber is provided with catalyst, and reformer chamber bottom and middle portion temperature are 300 DEG C ~ 420 DEG C;
The temperature on described reformer chamber top is 400 DEG C ~ 570 DEG C; Reformer chamber is connected by connecting line with separation chamber, all or part of top being arranged at reformer chamber of connecting line, and the high temperature by reformer chamber top continues the gas that heating exports from reformer chamber; Described connecting line, as the buffering between reformer chamber and separation chamber, makes the temperature of the gas exported from reformer chamber identical with the temperature of separation chamber or close;
Temperature in described separation chamber is set as 350 DEG C ~ 570 DEG C; Be provided with membrane separator in separation chamber, obtain hydrogen from the aerogenesis end of membrane separator;
Described raw material conveying device provides power, by the feedstock transportation in liquid container to hydrogen producer; Described raw material conveying device provides the pressure of 0.15 ~ 5MPa to raw material, and the hydrogen that hydrogen producer is obtained has enough pressure;
After described hydrogen producer starts hydrogen manufacturing, the hydrogen partial that hydrogen producer is obtained is or/and residual air is run by burning maintenance hydrogen producer;
The hydrogen that described hydrogen producer obtains is delivered to membrane separation device and is separated, and is more than or equal to 0.7MPa for separating of the difference of pressure inside and outside the membrane separation device of hydrogen;
Described membrane separation device is the membrane separation device at porous ceramic surface Vacuum Deposition palladium-silver, and film plating layer is palladium-silver, and the mass percent palladium of palladium-silver accounts for 75% ~ 78%, and silver accounts for 22% ~ 25%;
Obtained hydrogen is passed through transfer conduit real-time Transmission to power generation sub-system by described hydrogen manufacturing subsystem; Described transfer conduit is provided with air pressure adjustment subsystem, for adjusting the air pressure in transfer conduit; The hydrogen gas generation that described power generation sub-system utilizes hydrogen manufacturing subsystem obtained;
Described air pressure adjustment subsystem comprises microprocessor, gas pressure sensor, valve positioner, air outlet valve, outlet pipe; Described gas pressure sensor is arranged in transfer conduit, in order to respond to the barometric information in transfer conduit, and the barometric information of induction is sent to microprocessor; This barometric information received from gas pressure sensor and setting threshold interval are compared by described microprocessor; When the pressure data received is higher than the maximum in setting threshold interval, Microprocessor S3C44B0X valve positioner opens air outlet valve setting-up time, air pressure in transfer conduit is made to be in setting range, one end of outlet pipe connects air outlet valve simultaneously, the other end connects described hydrogen manufacturing subsystem, and the firing equipment that needs being hydrogen manufacturing subsystem by burning heats; When the pressure data received is lower than the minimum value in setting threshold interval, hydrogen manufacturing subsystem described in Microprocessor S3C44B0X accelerates the transporting velocity of raw material;
Described Collection utilization subsystem connects the Vent passageway of power generation sub-system, from the gas of discharging, collect water, utilizes the water collected as the raw material of hydrogen manufacturing subsystem, thus recycles;
Described Collection utilization subsystem comprises hydrogen separator, hydrogen check-valves, oxygen separator, oxygen check valve, is separated by hydrogen, oxygen is separated with water with water.
2. an instant hydrogen manufacturing electricity generation system, is characterized in that, described system comprises: hydrogen manufacturing subsystem, power generation sub-system, Collection utilization subsystem, and hydrogen manufacturing subsystem, power generation sub-system, Collection utilization subsystem connect successively;
Described hydrogen manufacturing subsystem utilizes methyl alcohol, water prepares hydrogen, and obtained hydrogen is used for generating by transfer conduit real-time Transmission to power generation sub-system;
Described Collection utilization subsystem connects the Vent passageway of power generation sub-system, from the gas of discharging, collect water, the raw material of water hydrogen manufacturing subsystem maybe will collected;
Described Collection utilization subsystem comprises air-water separator, the water collected is delivered to hydrogen manufacturing subsystem, thus recycles;
Described Collection utilization subsystem comprises hydrogen separator, hydrogen check-valves, and the Vent passageway of power generation sub-system connects the entrance of hydrogen separator, is provided with hydrogen check-valves in the pipeline that hydrogen separator exit connects; Described hydrogen separator is for separating of hydrogen and water;
Described Collection utilization subsystem also comprises hydrogen/oxygen separator, for separating of hydrogen and oxygen; Hydrogen/oxygen separator is arranged between described power generation sub-system Vent passageway and hydrogen separator;
Described Collection utilization subsystem comprises oxygen separator, oxygen check valve, for collecting oxygen;
The hydrogen that described Collection utilization subsystem is collected and oxygen for hydrogen manufacturing subsystem or/and power generation sub-system.
3. a preparing hydrogen, generating power method for the described instant hydrogen manufacturing electricity generation system of one of claim 1 to 2, it is characterized in that, described preparing hydrogen, generating power method comprises the steps:
Described hydrogen manufacturing subsystem utilizes methyl alcohol, water prepares hydrogen, obtained hydrogen is passed through transfer conduit real-time Transmission to power generation sub-system;
The hydrogen gas generation that described power generation sub-system utilizes hydrogen manufacturing subsystem obtained;
Described Collection utilization subsystem connects the Vent passageway of power generation sub-system, from the gas of discharging, collect water, the raw material of water hydrogen manufacturing subsystem maybe will collected.
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| CN107253699B (en) * | 2017-05-25 | 2019-07-26 | 北京东方华氢科技有限公司 | A kind of hydrogen preparation facilities |
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